Resin composition

ABSTRACT

A resin composition useful as a binder is provided comprising the reaction product of an amine derivative chosen from melamine, glycolurile or their mixtures with a C1 to C8 dialkoxyethanal, the reaction product is then reacted with a polyol.

This application is a continuation-in-part of 08/350,692 filed Dec. 7,1994, now U.S. Pat. No. 5,539,077.

BACKGROUND OF THE INVENTION

A non-formaldehyde alternative to phenol and melamine resins, which arebased on formaldehyde, has been desired because of regulatory and healthconcerns regarding formaldehyde. Due to the high performance, strengthand rigidity of these thermosetting formaldehyde-based resins inindustrial applications, replacement products maintaining suitableperformance have been difficult to find. This invention discloses aresin composition which performs in many applications likephenol-formaldehyde and melamine-formaldehyde resins, but contain nophenol or formaldehyde. These are thermosetting, film-formingcompositions which offer tensile strength, rigidity and water-resistancecomparable to the phenol-formaldehyde and melamine-formaldehyde resinsnow in use.

French Patent Application number 94-10186 filed Aug. 22, 1994 by SocieteFrancaise Hoechst discloses a novel aminoplast resin comprising thereaction product of an amine derivative such as melamine, glycolurile ortheir mixtures with an aldehyde of the formula R--CHO in which Rrepresents a dialkoxy methyl group, 1,3-dioxolan-2-yl possiblysubstituted up to 4 and/or 5 times by one or more alkyl groups(preferably up to C₄ alkyl), or a 1,3-dioxan-2-yl group possiblysubstituted up to 4, 5 and/or 6 times by one or more alkyl groups(preferably up to C₄ alkyl); in mixtures possibly with glyoxal. However,these aminoplast resins do not self-condense satisfactorily, formingfilms which are weak, brittle and water-sensitive. Attempts to hydrolyzethe acetal groups of these resins in order to increase their reactivityresulted in degradation of the melamine ring.

Thus it is an object of this invention to improve the aminoplast resinsas disclosed by French Patent Application No. 94-10186 to provide aresin which upon crosslinking provide films which are strong, hard,tough and water resistant. Applications for such improved resins includeuses as binders for non-woven substrates such as glass, polyester andnylon fibers used in building materials, air filters or scrub pads, aswell as for cellulose substrates such as automotive filters.

SUMMARY OF THE INVENTION

Briefly, the subject invention provides a resin composition comprisingthe reaction product of an amine derivative chosen from the groupconsisting of melamine, glycolurile or their mixtures with a C₁ to C₈dialkoxyethanal (which may also be referred to as a dialkoxyacetaldehydeor a glyoxal monoacetal), the reaction product is then mixed with apolyol having 2 or more hydroxyl groups. Optionally the amine derivativeand dialkoxyethanal can also be reacted with a dialdehyde, preferablyglyoxal. In a preferred embodiment the polyol is reacted with thereaction product.

DETAILED DESCRIPTION

The resin composition comprises a reaction product mixed with a polyol.The reaction product is the addition product of an amine derivative withdialkoxyethanal. The amine derivative is either melamine, glycolurile ora mixture thereof, with melamine preferred because the products providestronger and tougher films.

The C₁ -C₈ dialkoxyethanal is reacted with the amine derivativegenerally at a molar ratio of 1 to 6 equivalents of dialkoxyethanal tomelamine and 1 to 4 equivalents for glycolurile, preferably 2 to 4equivalents of dialkoxyethanal to the amine derivative. In addition adialdehyde, preferably glyoxal, can also be included in the reactionproduct in order to provide branching points in the molecular structure,and to promote a higher molecular weight. The dialdehyde is addedgenerally at a level of 0.05 to 3 preferably 0.5 to 1, molar equivalentsof aldehyde to the amine derivative.

The C₁ to C₈ dialkoxyethanal generally has the following formula:##STR1## wherein R₁ and R₂ are C₁ -C₈ alkyl or R₁ and R₂ are joined toform a cyclic dioxolano or a dioxano substituent. The C₁ to C₈dialkoxyethanol can also be described as a glyoxal monacetal in whichthe acetal is comprised of linear substituents or is a cyclic acetal.Preferably R₁ and R₂ are a C₁ -C₄ alkyl group, preferably the same groupand preferably a methyl group as this is the most economical derivativewhich is commercially available, manufactured by Societe FrancaiseHoechst and sold under the trademark Highlink DM (TM).

In addition to the reaction product a polyol having 2 or more hydroxylgroups is mixed in to form the resin composition. Suitable polyolsinclude dialkylene glycol, polyalkylene glycol, glycerin, alkoxylatedglycerin, polyvinyl alcohol, dextrose (and dextrose oligomers andderivatives), starch, starch derivatives, polyglycidol orpolysaccharrides (and derivatives). Preferred polyols are dipropyleneglycol, tripropoxylated glycerin, polyvinyl alcohol and mixturesthereof. The polyol is added at a level of at least 0.05 molarequivalents of polyol to the reaction product, preferably at least 0.1molar equivalents. Generally the resin composition comprises an amountof about 1% to 99%, with 15-50% preferred of polyol by weight (drybasis) of the resin composition. Through the addition of a polyol to thereaction product a resin is provided which upon crosslinking providesfilms which are strong, hard, tough and water resistant.

In a preferred embodiment the polyol is reacted with the reactionproduct. The resultant resin composition has been shown to havesignificantly improved properties, namely improvement in ambient tensileand hot wet tensile for a textile product using the resin composition asa binder where the polyol is reacted with the reaction product versesbeing mixed with the reaction product. Generally the polyol is reactedwith the reaction product under the following conditions: 75° to 110°C., or at reflux; at a pH of 4-7, preferably 5.5 to 6.5; and for a timeperiod of 0.5 to 5 hours, preferably 2-3 hours.

The addition of an acid catalyst to the resin composition is alsodesirable. Suitable catalysts are sulfuric acid, hydrochloric acid,phosphoric acid, p-toluene sulfonic acid, methane sulfonic acid,aluminum salts such as aluminum hydroxychloride and aluminum chloride,magnesium chloride, zirconium sulfate and zinc chloride and the like.These catalysts facilitate the reaction(s) which effects thecrosslinking. The acid catalyst is generally added in an amount of 0.1%to 15% preferably, 1% to 10% based on the weight (dry basis) of thereaction product.

The resin composition obtained herein contains neither phenol norformaldehyde but has been found to maintain the strength and integrityof phenolic resins under conditions of severe usage including hightemperature and water immersion. This resin composition is useful as abinder for cellulosic automotive oil filters, or for fiberglass in suchuses as fiberglass, textiles or insulation. The resin composition can beadded to a hydroxyl containing polymer (e.g. polyvinyl alcohol) whereinthe resin composition is used to crosslink the polymer.

EXAMPLE I

A reaction product of melamine with dimethoxyethanal was prepared asfollows: 12.6 g (0.1 mole) melamine was mixed at ambient temperaturewith 31.2 g (0.3 mole) of dimethoxyethanal in solution with 31.2 g ofwater and an amount of 30% soda (sodium hydroxide) for obtaining a pHaround 9. This mixture was then heated under agitation, for 2 hours at60° C. while maintaining the pH around 9 with adjustment, if necessary,with as many drops of 30% soda by weight as needed. This reactionproduct was a clear yellow liquid of 54% active solids after dilutionwith 6 g of water.

EXAMPLE II

A reaction product of melamine, glyoxal and dimethoxyethanal wasprepared as follows: 252 g (2 moles) melamine was mixed at ambienttemperature with 145 g (1 mole) glyoxal in aqueous solution at 40% byweight, 416 g (4 moles) dimethoxyethanal in solution with 277 g of waterand an amount of 30% soda by weight for obtaining a pH around 7. Themixture is next heated under agitation for 2 hours at 60° C. whilemaintaining the pH at around 7 by addition if necessary of as many dropsof 30% soda as needed. Approximately 1090 g of an aqueous solutioncontaining approximately 726 g of an aminoplast resin according to theinvention was obtained.

EXAMPLE III

A resin prepared as in Example II was comprised of 1 equivalent ofglyoxal, 2 equivalents of melamine and 4 equivalents of dimethoxyethanal(60% aqueous solution) reacted together. It was a clear, viscous liquidof 67% solids. A series of blends was prepared using this resin,p-toluene sulfonic acid (pTSA) in isopropanol (IPA, 1:1) as catalyst,and various amounts of either diethylene glycol (DEG) or dipropyleneglycol (DPG). Samples of these mixtures weighing 2.0 grams were curedfor 75 minutes at 130° C. and evaluated for film properties. Watersensitivity was evaluated by placing 0.5 g of crushed resin in aGardener viscosity tube and filling to the mark with deionized water.The tube was stoppered and shaken, then observed after 1 hour and colorrecorded on the Gardner scale. The formulations in Table 1 were used inthis example.

                  TABLE 1                                                         ______________________________________                                              A      B      C    D    E   F   G   H   J   J    K                      ______________________________________                                        Resin 10     10     10   10   10  10  10  10  10  10   10                     pTSA  0.6    0.6    0.6  0.6  0.6 --  0.6 0.6 0.6 0.6  0.6                    /IPA                                                                          DEG   5.80   2.90   1.96 0.98 --  --  --  --  --  --   --                     DPG   --     --     --   --   --  --  7.3 3.7 2.5 1.24 5.5                    ______________________________________                                        Results                                                                              Gardner                                                                Sample Color   Comments                                                       ______________________________________                                        A      18+     Hard, flexible film, black, didn't bubble, adhered to                         pan.                                                           B      4.5     Harder than A, strong, bubbled slightly, black,                               brittle.                                                       C      2.0     Hard, strong, bubbled. Very dark brown, brittle.               D      1.0     Similar to C, dark brown.                                      E      9.0     Very brittle, weak, amber, bubbled.                            F      6.5     Very brittle, weak, amber, bubbled less than E.                G      1.0     Dark brown, hard, strong, brittle.                             H      <1      Darker brown than G, hard, strong, brittle.                    I      <1      Very dark brown, hard, strong, brittle.                        J      <1      Black, hard, strong, less brittle.                             K      <1      Black, hard, strong, less brittle.                             ______________________________________                                    

These results show the resins utilizing DEG are sensitive to water, asevidenced by the development of color on the Gardner scale, while thoseemploying DPG are significantly more water resistant. The DPG resinsformed films similar in appearance to the DEG resins as far as color,hardness, brittleness and strength, but did not soften or discolor thewater upon prolonged soaking. Cured phenolic and melamine-formaldehyderesins are known for their resistance to water. Varying the amounts ofglycols also affects the degree of brittleness, strength and hardness.

EXAMPLE IV

A resin prepared as in Example I consisted of 3 molar equivalents ofdimethoxyethanal (DME) reacted onto 1 molar equivalent of melamine. Thisproduct was a clear, pale yellow liquid of 55% active solids. This resinwas evaluated as a replacement for melamine-formaldehyde resin as abinder on filter paper. The resin was evaluated alone and with variouspolyols according to the formulations of Table 2. Aluminum chloridesolution was found to be a suitable catalyst for the resin, but causedprecipitation of the melamine formaldehyde resin. Phosphoric acid wastherefore used as catalyst for the melamine formaldehyde resin. Thepolyols evaluated included Ethox PGW (glycerine reacted with 3equivalents of propylene oxide, from Ethox Corp., Greenville, S.C.)polyvinyl alcohol (fully hydrolyzed, ultra low molecular weight, such asAirvol 103, Air Products, Allentown, Pa. or Mowiol 3-98 or 4-98, HoechstCelanese Corp., Somerville, N.J.) or the same polyvinyl alcohol (PVOH)which has been reacted with 5% glyoxal. The formulations (by dry weight)of Table 2 were applied to Whatman filter paper, achieving a 19% add-on.The paper was dried and cured for 5 minutes at 177° C. (350° F.). Thepaper was tested for wet and dry Mullen Burst, wet and dry GurleyStiffness and tensile strength at ambient temperature, 105° C. (220°F.), 160° C. (320° F.) and 216° C. (420° F.). Results are displayed inTable 3.

                  TABLE 2                                                         ______________________________________                                                 A      B     C   D    E    F    G    H   I                           ______________________________________                                        Resin    95           90  70   70   70   70   70  70                          AlCl.sub.3 solution                                                                    5            10  5    5    5         5   5                           Melamine-       95                                                            formaldehyde                                                                  resin                                                                         H.sub.3 PO.sub.4                                                                              5                                                             PVOH/Glyoxal                   8.3       16.7 25                              PVOH                      8.3       16.7          25                          EthoxPGW                  16.7 16.7 8.3  8.3                                  ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                              A      B      C    D    E    F    G    H    I                           ______________________________________                                        Mullen,                                                                             8.0    8.8    8.8  11.6 15.0 6.6  12.2 15.0 13.8                        dry                                                                           (lbs) 0.8    9.6    5.6  7.8  14   9.4  11.0 9.4  10.4                        wet                                                                           Gurley,                                                                             526    606    428  482  511  562  562  555  526                         dry                                                                           (MD)                                                                          (mg)  295    348    304  266  215  273  229  222  237                         wet                                                                           Tensile,                                                                            8.3    7.4    5.9  8.6  9.2  7.9  8.9  9.7  9.1                         RT(Kg)                                                                        elon- 1.6    1.3    1.2  1.6  1.7  1.3  1.8  2.0  1.6                         gation,                                                                       105° C.                                                                      5.9    6.5    5.6  6.5  6.8  5.5  7.1  6.9  7.1                         elon- 1.1    1.2    1.0  2.1  4.4  1.7  1.3  1.5  2.0                         gation,                                                                       %                                                                             105° C.                                                                      5.6    4.4    4.6  5.4  6.5  5.0  4.8  7.1  5.3                         elon- 1.1    0.8    0.9  1.2  1.4  0.9  1.1  1.4  2.6                         gation,                                                                       %                                                                             215° C.                                                                      4.3    4.3    4.0  4.8  4.6  3.9  4.6  4.4  3.9                         elon- 1.3    1.2    1.3  2.2  3.1  1.0  1.4  1.4  1.3                         gation,                                                                       %                                                                             ______________________________________                                    

These results show that the melamine/DME resin by itself and incombination with various polyols, can achieve performance as a filterpaper binder comparable to or superior to a melamine/formaldehyde resin.These melamine/DME systems achieve this performance without use offormaldehyde. The presence of certain polyols are seen to provideperformance superior to the melamine/DME resin alone on paper.

EXAMPLE V

Various melamine/DME-polyol combinations were evaluated against amelamine/formaldehyde (MF) resin and a phenol/formaldehyde (PF) resin ascontrols. The MF resin is the same used in Example IV. The PF resin is aprecondensed aqueous resin having pH of 8.4, Brookfield viscosity of 760cps, solids (by refractive index) of 68% and 2% free formaldehyde. Theresins were padded onto Whatman filter paper, dried and cured at 350° F.(177° C.) for 5 minutes. The % add-on ranged from 19.6 to 20.4. Thephenolic resin readily dispersed in the aqueous pad bath, but coagulatedupon addition of catalyst. Therefore, it was applied without catalyst.The paper was tested for dry Mullen burst, Mullen burst after a 5 minuteboil, cross-directional tensile at ambient temperature, 220° F. (104°C.), 320° F. (160° C.), 420° F. (216° C.), and Gurley stiffness (MD andCD). Formulations are shown in Table 4 and results in Table 5.

                  TABLE 4                                                         ______________________________________                                                  1      2      3   4     5    6    7   8                             ______________________________________                                        Phenolic resin                                                                          100                                                                 MF resin         95                                                           Resin                   95  70    70   70   70  45                            AlCl.sub.3 soln.        5   5     5    5    5   5                             Ethox PGW                   16.7  16.7                                        PVOH/Glyoxal                      8.3  25       50                            PVOH                        8.3             25                                H.sub.3 PO.sub.4 5                                                            ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                                 1      2      3    4    5    6    7    8                             ______________________________________                                        Dry Mullen,                                                                            7.4    5.4    9.0  13.4 10.2 13.4 14.2 12.2                          Lbs                                                                           Boiled Mullen,                                                                         8.2    10.6   7.0  9.2  8.6  12.8 15.0 11.4                          Lbs                                                                           CD tensile,                                                                   Ambient                                                                       kg       6.6    5.4    4.5  6.0  5.4  6.7  7.7  7.4                           elongation, %                                                                          2.0    2.3    2.0  3.2  2.4  2.6  2.8  2.7                           220° F., Kg                                                                     5.5    3.9    4.2  4.4  3.7  5.6  5.8  5.7                           elongation, %                                                                          1.4    1.2    1.5  1.6  1.4  1.6  1.6  1.4                           320° F., Kg                                                                     5.4    3.6    3.6  4.3  3.9  4.9  5.5  5.3                           elongation, %                                                                          1.3    1.3    1.7  2.0  1.9  1.5  1.6  1.6                           420° F., Kg                                                                     3.9    2.8    3.6  3.5  3.1  4.0  4.1  4.0                           elongation, %                                                                          1.4    1.0    1.2  2.3  1.9  1.8  1.7  1.6                           Gurley                                                                        Stiffens, mg                                                                  Dry, MD  983    1036   629  681  629  747  784  650                              CD    836    703    518  562  459  611  622  533                           Wet, MD  888    895    451  282  355  371  384  200                              CD    723    526    362  251  266  282  266  193                           ______________________________________                                    

These data show that while the melamine/DME resin alone is comparable tothe MF, it is inferior to the phenolic resin. However, it is shown thatthe addition of certain polyols enhance the performance of themelamine/DME resin to the point of being comparable or superior to thephenolic resin in terms of burst and tensile. While the phenolic paperis stiffer than the melamine/DME paper, this is not necessarily adeficiency. Excessively stiff paper is brittle and more difficult tofold and flute to make an oil filter cartridge. This may require thefilter paper to be partially cured (B-staged), fabricated into thefluted cartridge shape and subsequently fully cured. The melamine/DMEresins may allow the advantage of being fully cured, yet not so brittleas to preclude folding. This could save a step in manufacturing.

EXAMPLE VI

To better understand the performance characteristics of the novel resincomposition, a cure profile study was done. Resin solutions were paddedonto Whatman filter paper at 20% add-on and air dried. The paper wasthen cured at 300° F. (149° C.), 350° F. (177° C.) or 400° F. (204° C.)for 0.5, 1, 2, 3 or 5 minutes. The paper was tested for ambient tensilestrength (cross direction), wet tensile and hot tensile (220° F./104°C.). The data indicate that the resins may be applied with a light orpartial cure, then fully cured at a subsequent treatment. This iscomparable to "B-Staging" a phenolic resin. It is also noteworthy thatsome of the samples show hot wet tensile retention that is 50% to 70% ofthe original ambient tensile. This is an indication of a full cure. Inthe data table below, the cure conditions are coded as follows: A-400°F., B-350° F. and C-300° F. Sample 2 was the resin with 5% aluminumchloride catalyst (see sample #3 of Table 4). Sample 3 was 70% resin, 5%aluminum chloride and 25% fully hydrolyzed, ultra low molecular weightPVOH (see sample #7 of Table 4).

                  TABLE 6                                                         ______________________________________                                        Hot (220° F.) Tensile, KG                                                      Time, min                                                             Sample  0.5        1.0   2.0      3.0 5.0                                     ______________________________________                                        3C      6.2        8.7   8.4      8.7 8.2                                     2C      3.8        5.3   5.1      5.5 4.9                                     3B      7.9        8.1   7.4      7.1 7.0                                     2B      4.1        5.8   5.5      5.0 5.8                                     3A      8.1        7.7   6.4      7.1 --                                      2A      4.4        5.3   3.9      5.0 --                                      ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Hot Wet Tensile, KG                                                                   Time, min                                                             Sample  0.5         1.0   2.0     3.0 5.0                                     ______________________________________                                        3C      0.08        3.0   4.3     3.5 4.2                                     2C      0.10        2.0   1.7     2.2 2.7                                     3B      0.13        4.2   5.0     5.2 4.3                                     2B      0.11        4.0   4.4     4.5 4.7                                     3A      0.10        5.1   5.5     5.0 --                                      2A      0.14        4.6   4.6     4.0 --                                      ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Ambient Tensile, KG                                                                   Time, min                                                             Sample  0.5       1.0    2.0     3.0  5.0                                     ______________________________________                                        3C      8.0       11.1   10.9    10.3 10.4                                    2C      5.2       6.8    6.7     6.5  6.5                                     3B      9.6       9.2    9.9     10.5 9.6                                     2B      4.6       7.6    7.3     7.7  7.2                                     3A      8.4       9.5    9.7     9.1  --                                      2A      4.4       7.3    6.5     6.9  --                                      ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        Ratio Of Hot Wet To Ambient Tensile                                                   Time, min                                                             Sample  0.5       1.0    2.0      3.0  5.0                                    ______________________________________                                        3C      0.01      0.27   0.39     0.34 0.40                                   2C      0.02      0.29   0.25     0.34 0.41                                   3B      0.01      0.46   0.50     0.49 0.44                                   2B      0.20      0.52   0.60     0.58 0.65                                   3A      0.01      0.54   0.57     0.55 --                                     2A      0.03      0.63   0.71     0.58 --                                     ______________________________________                                    

The testing results of Tables 6-9 show that time and cure temperaturecan be varied to provide a wet tensile to dry tensile ratio of 0.5 orhigher. This is considered "full cure".

EXAMPLE VII

The foregoing examples have shown that polyvinyl alcohol (PVOH) improvesthe performance of the Example I resin on paper. The Example I resinshould be a suitable crosslinking agent for various formulationscontaining PVOH or derivatives of PVOH or similarly hydroxylatedsubstrates. To this end, the Example I resin was utilized as acrosslinking agent for a PVOH/acrylic graft copolymer.

The graft copolymer consisted, on a dry basis, of 25% ultra lowmolecular weight, fully hydrolyzed PVOH grafted with 43.5% ethylacrylate, 0.75% butyl acrylate, 1.5% bis-phenol-A-diepoxydiacrylate and29.25% methyl methacrylate. The latex was a white, opaque dispersionwith a viscosity of 300 cps at 30% solids, with pH raised to 6.5 withammonium hydroxide. The formulations of Table 10 were applied tonon-woven polyester roofing mat and cured 3 minutes at 350° F.,achieving 23-24% add-on. The mat was tested for ambient tensile strengthand % elongation at 180° C. under loads ranging from 5 kg to 18 kg.Results are shown in Table 11. Sequabond® 145 (by Sequa Chemicals Inc.),a vinyl acetate/acrylic copolymer used commercially as a polymat roofingbinder was used as the control. High tensile strength and low elongationvalues are desirable properties.

                  TABLE 10                                                        ______________________________________                                                    A            B      C                                             ______________________________________                                        Sequabond 145                                                                             100          --     --                                            PVOH graft  --           100    78                                            AlCl.sub.3 soln.                                                                          --           --     4                                             Example I   --           --     18                                            % Add-On    23.5         23.6   23.7                                          ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                                       A           B      C                                           ______________________________________                                        Ambient tensile, Kg                                                                          26.6        31.4   26.1                                        % elongation   34.6        34.5   30.3                                        % Elongation@ 180° C.                                                  5 kg           6.1         4.0    3.1                                         8 kg           17.1        9.3    6.2                                         10 kg          24.9        14.1   9.3                                         12 kg          32.2        20.6   13.2                                        14 kg          39.0        30.3   17.7                                        16 kg          45.8        45.3   23.1                                        18 kg          53.0        66.1   30.3                                        ______________________________________                                    

The results of Table 11 show that the resin of Example I can serve as anon-formaldehyde crosslinker for PVOH graft lattices with equal orbetter performance than that seen in commercial lattices usingN-methylol acrylamide.

EXAMPLE VIII

The following examples show the added benefit derived from reacting theDME/Melamine resin with polyols, as opposed to blending them together.To a 1-liter, 3-necked flask fitted with a mechanical stirrer,thermometer and condenser was charged 477 grams of 60% aqueousdimethoxyethanal solution (2.75 moles), and 126 grams of melamine (1.00moles). The pH was raised to 9.5 with 5% sodium hydroxide (9.2 g). Thebatch was then heated to 58°-60° C. for 2 hours while maintaining the pHat 9.4-9.5 with 5% sodium hydroxide. A total of 39.3 grams of 5% sodiumhydroxide was added by syringe pump maintaining the pH in range duringthe reaction.

After the 2 hour reaction, 106.2 grams of glycerin tripropoxylate (GTP,0.4 moles) and 70.8 grams of dipropylene glycol (DPG, 1.5 moles) wereadded. The pH was adjusted to 6.5 with 0.3 grams of 40% sulfuric acidand heated to reflux (102° C.) for 2 hours, then cooled. The product wasa clear light amber color.

A similar product was made using a 3:1 molar ratio of DME to melaminewith comparable results.

EXAMPLE IX

The DME/melamine resins prepared in Example VIII which incorporated thepolyols during the reaction were compared to the condensed resin inwhich comparable amounts of the same polyols were added to (blendedinto) the formulation. These resins were applied to a non-reactivesubstrate (polyester non-woven mat) and compared for ambient tensile andhot wet tensile. The add-on was 20% and substrates were dried and curedfor 5 minutes at 350° F. The results below show significant improvementin ambient tensile and hot wet tensile for the reacted product vs. theblend.

    ______________________________________                                        DME/MELAMINE/POLYOL PRODUCTS ON POLYMAT                                                        A         B      C                                           ______________________________________                                        Al(OH) C12       3         3      3                                           3:1 DME/Mel, DPG, GTP                                                                          97                                                           reacted                                                                       3:1 DME/Mel resin          77                                                 DPG                        8                                                  GTP                        12                                                 2.75:1 DME/Mel, DPG, GTP          97                                          reacted                                                                       Tensile, MD, Kg  25.8      19.4   24.6                                        elongation, %    54.2      54.4   60.1                                        Hot wet tensile, MD, Kg                                                                        18.1      14.6   18.6                                        elongation, %    64.5      51.0   57.6                                        ______________________________________                                    

EXAMPLE X

To further illustrate the utility of this invention, adimethoxyethanal/melamine resin as described in Example I, was added atlevels of 6, 9, 12, and 18% of the total binder with 3% aluminum hydroxydichloride as catalyst, with the remainder being the PVOH graftcopolymer described in Example VII. The binder was applied at 22-24%add-on to a non-woven polyester roofing mat substrate, and cured for 3minutes at 350° F. The mat was tested for ambient tensile strength and %elongation at 180° C. under loads ranging from 5 to 18 kg. A commercial,high-performance vinyl-acrylic latex (Sequabond® 145 from SequaChemicals, Inc., Chester, S.C.) was used as a control. Results shownbelow in Table 12 show that while tensile remains fairly constant, %elongation at high temperature may be controlled by varying the amountof resin in the formulation.

                  TABLE 12                                                        ______________________________________                                        Product      1        2      3      4    5                                    ______________________________________                                        Sequabond ® 145                                                                        100                                                              PVOH Graft            79     85     88   91                                   DME/Melamine resin    18     12     9    6                                    Al(OH) Cl.sub.2       3      3      3    3                                    % add-on     23.9     22.8   23.5   23.4 22.8                                 Results                                                                       Ambient Tensile, Kg                                                                        29.6     29.8   27.9   29.5 29.5                                 % elongation 38.8     34.5   36.0   32.8 35.4                                 % ElongationΕ 180° C.                                          Load, Kg:                                                                     5            7.0      2.8    3.0    3.0  3.4                                  8            17.6     6.3    6.7    7.0  8.3                                  10           25.4     9.4    10.2   11.2 13.1                                 12           32.8     13.2   14.3   16.2 19.3                                 14           40.0     17.9   19.2   22.7 27.6                                 16           47.2     23.7   25.5   31.6 41.1                                 18           55.1     31.8   34.6   43.6 62.2                                 ______________________________________                                    

What is claimed is:
 1. A resin composition comprising:the reactionproduct of an amine derivative chosen from the group consisting ofmelamine, glycolurile or their mixtures with a C₁ to C₈ dialkoxyethanal;and a polyol having 2 or more hydroxyl groups which is reacted with saidreaction product.
 2. Resin composition of claim 1 wherein the reactionproduct comprises a molar ratio of 1 to 6 molar equivalents ofdialkoxyethanal to the melamine and 1 to 4 equivalents ofdialkoxyethanal to the glycolurile and comprises at least 0.05 molarequivalents of polyol to the reaction product.
 3. Resin composition ofclaim 2 wherein the reaction product comprises a molar ratio of 2 to 4molar equivalents of dialkoxyethanol to the amine derivative andcomprises at least 0.1 molar equivalents of polyol to the reactionproduct.
 4. Resin composition of claim 1 further comprising adialdehyde.
 5. Resin composition of claim 4 wherein the dialdehyde isglyoxal.
 6. Resin composition of claim 5 wherein the reaction productcomprises 0.05 to 3 molar equivalents of glyoxal to the aminederivative.
 7. Resin composition of claim 6 wherein the reaction productcomprises 0.5 to 1 molar equivalents of glyoxal to the amine derivative.8. Resin composition of claim 1 wherein the polyol is selected from thegroup consisting of dialkylene glycol, polyalkalene glycol, glycerine,alkoxylated glycerin, polyvinyl alcohol, dextrose, dextrose oligomers,polysaccharide derivatives, starch, starch derivatives, polyglycidol,polysaccharide, polysaccharide derivatives and their mixtures.
 9. Resincomposition of claim 8 comprising 1 to 99% by weight of polyol by weightof the resin composition.
 10. Resin composition of claim 9 wherein thepolyol as chosen from the group consisting of dipropylene glycol,tripropoxylated glycerin, polyvinyl alcohol and mixtures thereof. 11.Resin composition of claim 8 comprising 5 to 50% by weight of polyol byweight of the resin composition.
 12. Resin composition of claim 1further comprising an acid catalyst.
 13. Resin composition of claim 12comprising 0.1% to 15% of acid catalyst by weight of the reactionproduct.
 14. Resin composition of claim 13 wherein the acid catalyst ischosen from the group consisting of sulfuric acid, hydrochloric acid,phosphoric acid, p-toluene sulfonic acid, aluminum chloride, magnesiumchloride, zirconium sulfate, zinc chloride, methane sulfonic acid andaluminum hydroxychloride.
 15. Resin composition of claim 1 wherein theC₁ to C₈ dialkoxyethanal has the following formula: ##STR2## wherein R₁and R₂ are C₁ -C₈ alkyl or R₁ and R₂ are joined to form a cyclicdioxolano or a dioxano substituent.
 16. Resin composition of claim 15wherein R₁ and R₂ are C₁ -C₄ alkyl group.
 17. Resin composition of claim16 wherein R₁ and R₂ are a methyl group.
 18. Resin composition of claim16 wherein R₁ and R₂ are the same.
 19. Resin composition of claim 1further comprising a hydroxyl-containing polymer, wherein the resincomposition is used to crosslink said polymer.
 20. Process for binding asubstrate comprising applying the resin composition according to any ofclaims 1, 3, 6, 8, 12, 17 and 19 to a substrate, followed by curing theresin to crosslink the binder.
 21. Process of claim 20 wherein thesubstrate is chosen from the group consisting of glass, polyester,nylon, non-woven substrates and cellulose substrates.